Dynamic behavior of chiral sulfonimidoyl-substituted allyl and alkyl (dimethylamino)titanium(IV) complexes: Metallotropic shift, reversible β-hydride elimination/reinsertion, and ab initio calculations of allyl and alkyl aminosulfoxonium ylides

Journal of the American Chemical Society

Volumn 127, Issue 18, 2005, Pages 6617-6631

  Gais, Hans Joachim ^a   Bruns, Peter R ^a   Raabe, Gerhard ^a   Hainz, Rüdiger ^a   Schleusner, Marcel ^a   Runsink, Jan ^a   Babu, Gadamsetti S ^a  

^a RWTH AACHEN UNIVERSITY   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDES; CHEMICAL BONDS; COMPLEXATION; CONFORMATIONS; ELECTROSTATICS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; OLEFINS; SUBSTITUTION REACTIONS; TITANIUM COMPOUNDS;

BOND ROTATION; ELECTROSTATIC INTERACTIONS; ROOM TEMPERATURE; TOPOMERIZATION;

ORGANOMETALLICS;

ALLYLTITANIUM COMPLEX; TITANIUM; UNCLASSIFIED DRUG;

AB INITIO CALCULATION; ARTICLE; ATOM; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL STRUCTURE; CHIRALITY; COMPLEX FORMATION; CONFORMATION; CONJUGATION; ELECTRICITY; ELIMINATION REACTION; MOLECULAR DYNAMICS; PROTON NUCLEAR MAGNETIC RESONANCE; ROOM TEMPERATURE; STEREOCHEMISTRY;

EID: 18644385760     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0433828     Document Type: Article

References (106)

1. For reviews, see: (a) Duthaler, R. O.; Hafner, A. Chem. Rev. 1992, 92, 807-832.
2. (b) Hoppe, D. In Stereoselective Synthesis, Methods of Organic Chemistry (Houben-Weyl); Helmchen, G., Hoffmann, R. W., Mulzer, J., Schaumann, E., Eds., Thieme: Stuttgart, 1996; E21, Vol. 3, pp 1551-1602.
3. (c) Pyne, S. G. Sulfur Rep. 1999, 21, 281-334.
4. (d) Sato, F.; Urabe, H.; Okamoto, S. Chem. Rev. 2000, 100, 2835-2886.
5. (e) Denmark, S. E.; Almstead, N. G. In Modern Carbonyl Chemistry; Otera, J., Ed.; Wiley-VCH: Weinheim, 2000; pp 293-394.
6. (f) Reggelin, M.; Zur, C. Synthesis 2000 1, 1-64.
7. (g) Szymoniak, J.; Moise, C. In Titanium and Zirconium in Organic Synthesis; Marek, I., Ed.; Wiley-VCH: Weinheim, 2002; pp 451-474.
8. (h) Mikami, K.; Matsumoto, Y.; Spiono, T. In Science of Synthesis, Methods of Molecular Transformations (Houben-Weyl); Imamoto, T., Noyori, R., Eds., Thieme: Stuttgart, 2003; Vol. 2, pp 457-679.
9. For recent examples, see: (a) Okamoto, S.; Teng, X.; Fujii, S.; Takayama, Y.; Sato, F. J. Am. Chem. Soc. 2001, 123, 3462-3471.
10. (b) Gaul, C.; Seebach, D. Helv. Chim. Acta 2002, 85, 963-978.
11. (c) BouzBouz, S.; Cossy, J. Org. Lett. 2003, 5, 3029-3031.
12. (f) Reuber, J.; Fröhlich, R.; Hoppe, D. Org. Lett. 2004, 6, 783-786.
13. (d) Schleth, F.; Vogler, T.; Harms, K.; Studer, A. Chem. Eur. J. 2004, 10, 4171-4185.
14. (e) Adam, J.-M.; de Pays, L.; Laguerre, M.; Ghosez, L. Tetrahedron 2004, 60, 7325-7344.
15. (a) Hainz, R.; Gais, H.-J.; Raabe, G. Tetrahedron: Asymmetry 1996, 7, 2505-2508.
16. (b) Hainz, R. Ph.D. Thesis, RWTH Aachen, 1998.
17. (c) Gais, H.-J.; Hainz, R.; Müller, H.; Bruns, P. R.; Giesen, N.; Raabe, G.; Runsink, J.; Nienstedt, S.; Decker, J.; Schleusner, M.; Hachtel, J.; Loo, R.; Woo, C.-W.; Das, P. Eur. J. Org. Chem. 2000, 3973-4009.
18. (d) Schleusner, M. Ph.D. Thesis, RWTH Aachen, 2002.
19. (e) Bruns, P. R. Ph.D. Thesis, RWTH Aachen, 2003.
20. (a) Schleusner, M.; Gais, H.-J.; Koep, S.; Raabe, G. J. Am. Chem. Soc. 2002, 124, 7789-7800.
21. (b) Koep, S.; Gais, H.-J.; Raabe, G. J. Am. Chem. Soc. 2003, 125, 13243-13251.
22. (c) Günter, M.; Gais, H.-J. J. Org. Chem. 2003 68, 8037-8041.
23. (d) Gais, H.-J.; Loo, R.; Das, P.; Raabe, G. Tetrahedron Lett. 2000, 41, 2851-2854.
24. (e) Gais, H.-J.; Loo, R.; Roder, D.; Das, P.; Raabe, G. Eur. J. Org. Chem. 2003, 1500-1526.
25. (f) Gais, H.-J.; Reddy, L. R.; Babu, G. S.; Raabe, G. J. Am. Chem. Soc. 2004, 126, 4859-4864.
26. (g) Gais, H.-J.; Babu, G. S.; Günter, M.; Das, P. Eur. J. Org. Chem. 2004, 1464-1473.
27. (h) Reddy, L. R.; Gais, H.-J.; Woo, C.-W.; Raabe, G. J. Am. Chem. Soc. 2002, 124, 10427-10434.
28. (i) Gais, H.-J.; Müller, H.; Decker, J.; Hainz, R. Tetrahedron Lett. 1995, 36, 7433-7436.
29. (j) Tiwari K. S.; Schneider, A.; Gais, H.-J. Tetrahedron Lett. 2004, 45, 8343-8346.
30. For the synthesis of chiral sulfonimidoyl-substituted allyl tris(isopropoxy)-titanium(IV) complexes, which carry a further chiral substituent at the N atom, and their highly successful application in asymmetric synthesis, see: (a) Reggelin, M.; Weinberger, H. Angew. Chem. 1994, 106, 489-491;
31. Reggelin, M.; Weinberger, H. Angew. Chem., Int. Ed. Engl. 1994, 33, 444-446.
32. (b) Reggelin, M.; Weinberger, H.; Gerlach, M.; Welcker, R. J. Am. Chem. Soc. 1996, 118, 4765-4777.
33. (c) Reggelin, M.; Weinberger, H.; Heinrich, T. Liebigs Ann./ Recl. 1997, 1881-1886.
34. (d) Reggelin, M.; Heinrich, T. Angew. Chem. 1998, 110, 3005-3008;
35. Reggelin, M.; Heinrich, T. Angew. Chem., Int. Ed. 1998, 37, 2883-2886.
36. (e) Reggelin, M.; Gerlach, M.; Vogt, M. Eur. J. Org. Chem. 1999, 1011-1031.
37. (a) Cyclic complexes of type I and IV, whose double bond is embedded in a carbocyclic ring, show the same diversity in reactivity.
38. (b) Gais, H.-J.; Babu, G. S., unpublished.
39. (a) Gais, H.-J.; Müller, H.; Bund, J.; Scommoda, M.; Brandt, J.; Raabe, G. J. Am. Chem. Soc. 1995, 117, 2453-2466.
40. (b) Scommoda, M.; Gais, H.-J.; Bosshammer, S.; Raabe, G. J. Org. Chem. 1996, 61, 4379-4390.
41. (c) Brandt, J.; Gais, H.-J. Tetrahedron: Asymmetry 1997, 8, 909-912.
42. (a) Gais, H.-J.; Lenz, D.; Raabe, G. Tetrahedron Lett. 1995, 36, 7437-7440.
43. (b) Lenz, D. Ph.D. Thesis, RWTH Aachen. 1995.
44. Bordwell, F. G.; Branca, J. C.; Johnson, C. R.; Vanier, N. R. J. Org. Chem. 1980, 45, 3884-3889.
45. For the intramolecular 1,4-coordination of a sulfonyl O atom to a Ti atom, see: (a) Gais, H.-J.; Vollhardt, H. J.: Lindner, H. J.; Paulus, H. Angew. Chem. 1988, 100, 1598-1600;
46. Gais, H.-J.; Vollhardt, H. J.: Lindner, H. J.; Paulus, H. Angew. Chem., Int. Ed. Engl. 1988, 27, 1540-1542.
47. (b) Royo, E.; Betancort, J. M.; Davis, T. J.; Carroll, P.; Walsh, P. J. Organometallics 2000, 19, 4840-4851.
48. 13C-NMR- Spektroskopie; Thieme: Stuttgart, 1984.
49. 1J(C,H) for Cl of a carbanion on changing its coordination geometry from a tetrahedral to a planar, see: Reich, H. J.; Dykstra, R. R. J. Am. Chem. Soc. 1993, 115, 7041-7042.
50. (a) Neese, H.-J.; Bürger, H. J. Organomet. Chem. 1971, 32, 213-222.
51. (b) Panse, M.; Thiele, K.-H. Z. Anorg. Allg. Chem. 1982, 485, 7-14.
52. (c) Hafner, A.; Duthaler, R. O.; Marti, R.; Rihs, G.; Rothe-Streit, P.; Schwarzenbach, F. J. Am. Chem. Soc. 1992, 114, 2321-2336.
53. (d) Duthaler, R. O.; Hafner, A.; Alsters, P. L.; Bold, G.; Rihs, G.; Rothe-Streit, P.; Wyss, B. Inorg. Chim. Acta 1994, 222, 95-113.
54. (e) Balaich, G. J.; Hill, J. E.; Waratuke, S. A.; Fanwick, P. E.; Rothwell, I. P. Organometallics 1995, 14, 656-665.
55. (f) Andrés, R.; Galakhov, M.; Gómez-Sal, M. P.; Martín, A.; Mena, M.; Santamaría, C. J. Organomet. Chem. 1996, 526, 135-143.
56. (g) Ray, B.; Neyroud, T. G.; Kapon, M.; Eichen, Y.; Eisen, M. S. Organometallics 2001, 20, 3044-3055.
57. (h) Qian, X.; Huang, J.; Qian, Y. J. Organomet. Chem. 2004, 689, 1503-1510.
58. Johnson, C. R.; Schroeck, C. W. J. Am. Chem. Soc. 1973, 95, 7418-7423.
59. For NMR data of sulfur ylides, see: (a) Schmidbaur, H.; Kammel, G. Chem. Ber. 1971, 104, 3234-3240.
60. (b) Barbella, G.; Dembech, P.; Garbesi, A. Tetrahedron Lett. 1980, 21, 2109-2112.
61. (c) Pörschke, K.-R. Chem. Ber. 1987, 120, 425-427.
62. (d) Aggarwal, V. K.; Schade, S.; Taylor, B. J. Chem. Soc., Perkin Trans. 1 1997, 2811-2813.
63. 3- allyltitan(III) complexes, see: (a) Chen, J.; Kai, Y.; Kasai, N.; Yasuda, H. J. Organomet. Chem. 1991, 407, 191-205.
64. (b) Greidanus, G.; McDonald, R.; Stryker, J. M. Organometallics 2001, 20, 2492-2504
65. (a) Radius. U.; Sundermeyer, J.; Peters, K.; von Schnering, H.-G. Eur. J. Inorg. Chem. 2001, 1617-1623.
66. (b) Čermák, J.; St'astná, L.; Sýtora, J.; Císařová, I.; Kvíčala, J. Organometallics 2004, 23, 2850-2854.
67. (a) Vrieze, K. In Dynamic Nuclear Magnetic Resonance Spectroscopy; Jackman, L. M., Cotton, F. A., Eds.; Academic Press: New York, 1975; pp 441-487.
68. (b) Reetz, M. T.; Steinbach, R.; Westermann, J.; Peter, R.; Wenderoth, B. Chem. Ber. 1985, 118, 1441-1454.
69. (c) Kasatkin, A.; Nakagawa, T.; Okamoto, S.; Sato, F. J. Am. Chem. Soc. 1995, 117, 3881-3882.
70. For structural studies of allylzirconium(IV) complexes, see: (a) Larson, E. J.; Van Dort, P. C.; Lakanen, J. R.; O'Neill, D. W.; Pederson, L. M.; McCandless, J. J.; Silver, M. E.; Russo, S. O.; Huffman, J. C. Organometallics 1988, 7, 1183-1187.
71. (b) Vance, P. J.; Prins, T. J.; Hauger, B. E.; Silver, M. E.; Wemple, M. E.; Pederson, L. M.; Kort, D. A.; Kannisto, M. R.; Geerligs, S. J.; Kelly, R. S.; McCandless, J. J.; Huffman, J. C.; Peters, D. G. Organometallics 1991, 10, 917-924.
72. Seeman, J. L. Chem. Rev. 1983, 83, 83-134.
73. SPh* interaction (cf. Figures 8 and 9) in the chair-like TS.
74. Mikołajczk, M.; Drabowicz, J.; Kiełbasiński, P. Chiral Sulfur Reagents; CRC Press: Boca Raton, 1997.
75. All quantum-chemical calculations have been performed with: Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, Jr., J. A.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Salvador, P.; Dannenberg, J. J.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; D. J. Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, Revision A.11; Gaussian, Inc.: Pittsburgh, PA, 2001.
76. Wiberg, K. B.; Castejon, H. J. Am. Chem. Soc. 1994, 116, 10489-10497.
77. Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899-926.
78. Glendening, E. D.; Reed, A. E.; Carpenter, J. E.; Weinhold, F. NBO 3.0 Program Manual; Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin: Madison, WI 53706.
79. Raabe, G.; Gais, H.-J.; Fleischhauer, J. J. Am. Chem. Soc. 1996, 118, 4622-4630, and references therein.
80. (a) Akita, M.; Yasuda, H.; Nagasuna, K.; Nakamura, A. Bull. Chem. Soc. Jpn. 1983, 56, 554-558.
81. (b) Cohen, S. A.; Auburn, P. R.; Bercaw, J. E. J. Am. Chem. Soc. 1983, 105, 1136-1143.
82. (c) Thorn, M. G.; Hill, J. E.; Waratuke, S. A.; Johnson, E. S.; Fanwick, P. E.; Rothwell, I. P. J. Am. Chem. Soc. 1997, 119, 8630-8641.
83. (d) Baumann, R.; Stumpf, R.; Davis, W. M.; Liang, L.-C.; Schrock, R. R. J. Am. Chem. Soc. 1999, 121, 7822-7836.
84. (e) de Meijere, A.; Kozhushkov, S. I.; Savchenko, A. I. In Titanium and Zirconium in Organic Synthesis; Marek, I., Ed.; Wiley-VCH: Weinheim, 2002; pp 390-434.
85. (a) Cummins, C. C.; Schrock, R. R.; Davis, W. M. Organometallics 1992, 11, 1452-1454.
86. (b) Nöth, H.; Schmidt, M. Organometallics 1995, 14, 4601-4610.
87. (c) Bennett, J. L.; Wolczanski, P. T. J. Am. Chem. Soc. 1997, 119, 10696-10719.
88. (d) Turculet, L.; Tilley, T. D. Organometallics 2004, 23, 1542-1553.
89. (a) Schrock, R. R.; Parshall, G. W. Chem. Rev. 1976, 76, 243-268.
90. (b) Davidson, P. J.; Lappert, M. F.; Pearce, R. Chem. Rev. 1976, 76, 219-242.
91. (c) Reetz, M. Organotitanium Reagents in Organic Synthesis; Springer-Verlag: Berlin, 1986.
92. (d) Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principles and Application of Organotransition Metal Chemistry; University Science Books: Mill Valley, CA, 1987.
93. (e) Brookhart, M.; Green, M. L. H.; Wong, L.-L. In Progress in Inorganic Chemistry; Lippard, S. J., Ed.; Wiley: New York, 1988; Vol. 36, pp 1-124.
94. (f) Bochmann, M. In Comprehensive Organometallic Chemistry II; Abel, E W., Stone, F. G. A., Wilkinson, G., Lappert, M. F., Eds.; Pergamon; Oxford, 1995; Vol. 4, pp 273-421.
95. (a) Green, M. L. H.; Sella, A.; Wong, L.-L. Organometallics 1992, 11, 2650-2659.
96. (b) Tempel, D.; Brookhart, M. Organometallics 1998, 17, 2290.
97. (c) Umezawa-Vizzini, K.; Lee, T. R. Organometallics 2004, 23, 1448-1452.
98. For the observation of a reversible alkene extrusion upon reaction of an alkyltitanium(III) complex with alkenes, which proceeds via an intermediate titamum(III) hydride, see: Luinstra, G. A.; Voegelzang, J.; Teuben, J. H. Organometallics 1992, 11, 2273-2281.
99. (a) Gais, H.-J.; Erdelmeier, I.; Lindner, H. J.; Vollhardt, J. Angew. Chem. 1986, 98, 914-915;
100. Gais, H.-J.; Erdelmeier, I.; Lindner, H. J.; Vollhardt, J. Angew. Chem., Int. Ed. Engl. 1986, 25, 938-939.
101. (b) Gais, H.-J.; Dingerdissen, U.; Krüger, C.; Angermund, K. J. Am. Chem. Soc. 1987, 109, 3775-3776.
102. (c) Müller, J. F. K.; Batra, R.; Spingler, B.; Zehnder, M. Helv. Chim. Acta 1996, 79, 820-826.
103. (d) Müller, J. F. K.; Neuburger, M.; Spingler, B. Angew. Chem. 1999, 111, 3766-3769;
104. Müller, J. F. K.; Neuburger, M.; Spingler, B. Angew. Chem., Int. Ed. 1999, 38, 3549-3552.
105. The 1,3-C,N-shift of the Li atom of 15 could also take place within a cyclic eight-membered dimer of 15, the Li atoms of which are each coordinated by a Ć atom and a N atom; see ref 32a. Alternatively, the topomerization of the hydrogens of the methylene groups could proceed within an ion pair formed through dissoziation of 15.
106. Schöllkopf, U. In Methoden der Organischen Chemie (Houben-Weyl); Müller, E., Ed.; Thieme: Stuttgart, 1970; Bd. XIII/1, pp 86-251.